Trans,trans-Δ-damascone, mixtures containing major proportions of same, processes for preparing same and organoleptic uses thereof

ABSTRACT

Described is the compound trans, trans-Δ-damascone and mixtures of trans, trans-Δ-damascone and its isomer, cis, trans-Δ-damascone is in a major proportion, a process for preparing same and processes for adding such trans, trans-Δ-damascone or such mixtures containing high proportions of trans, trans-Δ-damascone to consumable materials whereby: 
     (i) In foodstuffs, medicinal products, chewing gums, toothpastes and chewing tobacco, sweet, floral, rose-like, raspberry-like, fruity, cooked plum, grape juice-like, apple juice-like and winey aroma and flavor characteristics are augmented or enhanced; 
     (ii) In perfumes, perfumed articles and colognes, rose, berry, apple, green and sweet floral notes are imparted, augmented and/or enhanced; and 
     (iii) In tobaccos, tobacco flavor, substitute tobaccos and substitute tobacco flavor and aroma imparting, enhancing or augmenting compositions, floral, musty, hay-tea-like, sweet and fruity aroma and taste nuances both prior to and on smoking 
     and flavor compositions and perfume compositions containing trans, trans-Δ-damascone and mixtures containing a high proportion of trans, trans-Δ-damascone and a low proportion of cis, trans-Δ-damascone or no cis, trans-Δ-damascone.

This is a divisional of application Ser. No. 928,718, filed July 27,1978.

BACKGROUND OF THE INVENTION

The present invention provides the compound trans, trans-Δ-damasconehaving the structure: ##STR1## wherein the dashed line represents a"trans" configuration of the crotonyl moiety with respect to themonomethyl moiety bonded to the cyclohexene group and mixturescontaining a high proportion of trans, trans-Δ-damascone (more than 50%)and low proportion of cis, trans-Δ-damascone having the structure:##STR2## and a straightforward, economical process directed towardssynthesizing trans, trans-Δ-damascone and mixtures containing a highproportion of trans, trans-Δ-damascone by means of the followingreaction sequence: ##STR3## and utilization of trans, trans-Δ-damasconeand mixtures containing a high proportion of trans, trans-Δ-damasconeand low proportion of cis, trans-Δ-damascone for their organolepticproperties in perfumes, perfumed articles, foodstuffs, foodstuffflavoring compositions, chewing gums, toothpaste, medicinal products,tobaccos, tobacco flavoring compositions, substitute tobaccos andsubstitute tobacco flavoring compositions.

In the perfumery art, there is a considerable need for substituentshaving rose, berry, apple, green and sweet floral notes. Floral, musty,hay-tea-like, sweet and fruity notes are desirable in tobacco flavoringcompositions and substitute tobacco flavoring compositions. Specificallydescribed herein are materials having such an organoleptic profile butwhich do not discolor with age. Such fragrance materials have a wideutilization in the presence of these perfume compounds. A limited amountof such materials that give rise to these properties is available fromnatural sources but the natural materials are subject to wide variationsin quality, are expensive, and are often in critically short supply. Thesame holds true for the use of trans, trans-Δ-damascone or mixturescontaining a high proportion of trans, trans-Δ-damascone and lowproportion of cis, trans-Δ-damasone for use in tobacco or for use intobacco substitutes.

In addition, there is a continuing search for food flavor compositionswhich can vary, fortify, modify, enhance, augment or otherwise improvethe flavor and/or aroma of foodstuffs, medicinal products, toothpastesand chewing gums. To be satisfactory, such compositions should bestable, non-toxic and blendable with other ingredients to provide theirown unique flavor and aroma nuances without detracting from theco-ingredients. Preferably, such compositions should be naturallyoccurring or present in natural foodstuffs so that their ingestiblesafety can be readily recognized. These materials should be capable ofbeing synthesized in a simple and economical manner. The need for safeflavors in the berry fruit flavor area, especially the raspberry area,winey area, juice area (more especially, grape, tea and mimosa) is wellknown particularly in the ice cream and yogurt flavor areas. Morespecifically, there is a need for the development of non-toxic materialswhich can replace natural materials not readily available, having seet,floral, rose-like, raspberry-like, fruity, cooked plum, grapejuice-like, apple juice-like and winey aroma and flavor characteristics.

The instant invention provides the foregoing, which the prior art hasheretofore failed to provide. Furthermore, nothing in the prior artshows the unexpected, unobvious and advantageous value of the compoundhaving the structure: ##STR4## although mixtures presumed to bepredominantly cis, trans-Δ-damascone with minor amounts of trans,trans-Δ-damascone have been produced by Ayyar, Cookson and Kagi as setforth in J. Chem. Soc., Perkin Trans. 1, 1975 (17) 1727-36 [title:"Synthesis ofδ-Damascone[trans-1-(2,6,6-Trimethylcyclohex-3-enyl)but-2-en-1-one] andβ-Damascenone[trans-1-(2,6,6-Trimethylcyclohexa-1,3-dienyl)but-2-en-1-one]"].The reaction sequence of the Ayyar synthesis of compositions presumed tobe predominantly cis, trans-Δ-damascone with minor amounts of trans,trans-Δ-damascone is as follows: ##STR5## wherein the wavy line isrepresentative of a "cis" or "trans" configuration of the methyl moietywith respect to the acetyl or crotonoyl moiety, both of which are bondedto the cyclohexenyl moiety, the "cis" isomer presumably being the majorisomer and the "trans" isomer presumably being the minor isomer in thisreaction sequence.

Ayyar, et al. fails to teach the unexpected, unobvious significanceattached to the trans, trans-Δ-damascone as discovered in the instantinvention.

On the other hand, in U.S. Pat. No. 3,956,392 at column 7 and 8, it isindicated that trans, e-1-crotonyl-2,2,6-trimethylcyclohexane (totallysaturated insofar as the ring moiety is concerned) has unexpected,unobvious properties over cis, e-1-crotonyl-2,2,6-trimethylcyclohexane;e-β-damascenone and e-β-damascone. It is noteworthy that whereas trans,trans-Δ-damascone of our invention has a sweet, floral, rose-like,raspberry, fruity, cooked plum, grape juice-like, apple juice-like,winey aroma and flavor character at 0.05 ppm with a threshold of 0.002ppm, the corresponding cis, trans-Δ-damascone which is presumed to bethe Ayyar, et al product has a rose-like, fruity, raspberry-like, rosey,spiced apple-like, tobacco, winey and clove aroma character with a rose,fruity, raspberry, rosey, spiced apple, tobacco, winey and tea flavorcharacter at 0.05 ppm with a threshold of 0.005 ppm. The comparison oftrans, trans-Δ-damascone with cis, trans-Δ-damascone, which is presumedto be the Ayyar, et al product, is much more dramatic with respect tothe perfumery properties of trans, trans-Δ-damascone as is shown in theexamples set forth infra.

Swiss Pat. No. 537,352 issued on July 13, 1973 discloses1(2-butenyl)cyclohexenes having the structure: ##STR6## and this SwissPatent is abstracted in Chem. Abstracts 79:104808s.

However, none of the foregoing references discloses trans,trans-Δ-damascone or mixtures containing a high percentage of trans,trans-Δ-damascone and a less than 50% quantity of cis, trans-Δ-damasconeor their uses in foodstuffs, perfumes, perfumed articles, tobaccos, andsubstituted tobaccos for their organoleptic properties.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the NMR spectrum for cis, trans-Δ-damascone producedaccording to the process of Example I.

FIG. 2 represents the Infrared spectrum for cis, trans-Δ-damasconeproduced according to the process of Example I.

FIG. 3 represents the NMR spectrum for trans, trans-Δ-damascone producedaccording to the process of Example II.

FIG. 4 represents the Infrared spectrum for trans, trans-Δ-damasconeproduced according to the process of Example II.

THE INVENTION

The present invention provides the compound trans, trans-Δ-damasconehaving the structure: ##STR7## wherein the dashed line represents a"trans" configuration of the crotonyl moiety with respect to themonomethyl moiety bonded to the cyclohexene group and mixturescontaining a high proportion of trans, trans-Δ-damascone (more than 50%)and low proportion of cis, trans-Δ-damascone having the structure:##STR8## and a straightforward, economical process directed towardssynthesizing trans, trans-Δ-damascone and mixtures containing a highproportion of trans, trans-Δ-damascone by means of the followingreaction sequence: ##STR9##

Trans, trans-Δ-damascone as well as mixtures containing a highproportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone are capable of augmenting or enhancing berry fruitflavors especially raspberry flavors, wine flavors, tea flavors andjuice flavors, especially grape and mimosa flavors, by imparting theretosweet, floral, damascenone-like, raspberry-like, fruity, cooked plum,grape juice-like and apple juice-like aroma and flavor characteristics.

The compound trans, trans-Δ-damascone as well as mixtures containing ahigh proportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone are also capable of modifying or enhancing the odorcharacteristics of perfume compositions, colognes and perfumed articlesby imparting thereto sweet floral, rose, berry, apple and greenfragrance notes, thus fulfilling a need in the field of perfumery.

In tobacco, tobacco flavoring compositions, substitute tobacco andsubstitute tobacco flavoring compositions, the compound trans,trans-Δ-damascone as well as mixtures containing more than 50% trans,trans-Δ-damascone, and less than 50% cis, trans-Δ-damascone, impartfloral, musty, hay-tea-like and sweet/fruity notes prior to and onsmoking.

Trans, trans-Δ-damascone of our invention is produced by first preparing1-α-acetyl-2-β, 6,6-trimethyl-3-cyclohexane by means of treatment of1-α-acetyl-2-α, 6,6-trimethyl-3-cyclohexane (prepared according to Ayyaret al., cited supra) with refluxing alcoholic base or alkali metalalcoholate according to the reaction: ##STR10## wherein R is loweralkyl, e.g., methyl or ethyl and M is alkali metal, e.g., sodium orpotassium.

From a practical standpoint, the starting material is a compositionconsisting of 80-90% of the cis isomer of1-acetyl-2,6,6-trimethyl-3-cyclohexene (referred to also as1-α-acetyl-2-α,6,6-trimethyl-3-cyclohexene) and about 10-20% of thetrans isomer (also referred to as1-α-acetyl-2-β,6,6-trimethyl-3-cyclohexene). Also from a practicalstandpoint, the resulting product contains a minor proportion of the cisisomer (approximately 10-20%) and a major proportion of the trans isomer(approximately 80-90%).

The resulting trans isomer of 1-acetyl-2,6,6-trimethyl-3-cyclohexene,preferably the mixture containing about 80-98% of this trans isomer andabout 2-20% of the cis isomer may be distilled to form an essentiallypure trans isomer or may be used "as is" in the subsequent reaction. Thesaid trans isomer is reacted with acetaldehyde according to the methodof Ayyar, et al cited supra to give a hydroxy ketone having thestructure: ##STR11## The resulting product is then dehydrated usingstandard dehydrating reagents as disclosed by Ayyar, et al. cited supra,such as, paratoluenesulfonic acid or acetic anhydride thereby producingthe desired trans, trans-Δ-damascone according to the reaction:##STR12## The reaction product is then distilled from the reaction mass.From a practical and economical standpoint, the distilled reactionproduct is used as is for its organoleptic properties and this reactionproduct contains 80-98% trans, trans-Δ-damascone and 2-20% cis,trans-Δ-damascone having the structure: ##STR13## when the startingmaterial, the trans isomer of 1-acetyl-2,6,6-trimethyl-3-cyclohexene isan 80-98% mixture also containing "cis" isomer; but the reaction productmay be in "pure" form when the starting material is "pure"trans-1-acetyl-2,6,6-trimethyl-3-cyclohexene.

When produced as the aforementioned mixture, the two isomers having thestructures: ##STR14## may be separated using preparative GLC.

The ranges of conditions of the foregoing reactions are the same asthose specified by Ayyar, Cookson and Kagi in the paper entitled:"Synthesis ofδ-Damascone[trans-1-(2,6,6-Trimethylcyclohex-3-enyl)but-2-en-1-one] andβ-Damascenone[trans-1-(2,6,6-Trimethylcyclohexa-1,3-dienyl)but-2-en-1-one]",J.Chem.Soc., Perkins Trans. 1, 1975 (17) 1727-36 in setting forth theproduction of trans-1-(6,6-dimethylcyclohexa-1,3-dienyl)but-2-en-1-one(see page 1736 of Ayyar, et al). The ranges of conditions of theforegoing reactions are also exemplified in the examples infra.

When the compound trans, trans-Δ-damascone or the mixture containing ahigh proportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone of our invention are used as food flavor adjuvants,the nature of the co-ingredients included with the trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone used informulating the product composition will also serve to alter, modify,augment or enhance the organoleptic characteristics of the ultimatefoodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschickle, or substitutes therefor, including jelutong, guttakay, rubberor certain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the compound trans, trans-Δ-damascone or compositioncontaining a high proportion of trans, trans-Δ-damascone and less than50% cis, trans-Δ-damascone of our invention, and in addition, sweeteningagents which may be sugars, including sucrose or dextrose and/orartificial sweeteners such as cyclamates or saccharin. Other optionalingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal,beta, beta-dimethylacrolein, methyl-n-amyl ketone, n-hexenal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptanal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methyl furfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene,1-phellandrene, p-cymene, 1-alphapinene; pyrazines such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, acetoin and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the compound trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone of ourinvention by not covering or spoiling the organoleptic properties (aromaand/or taste) thereof; (ii) be non-reactive with the compound trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone of ourinvention and (iii) be capable of providing an environment in which thecompound trans, trans-Δ-damascone or composition containing a highproportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone of our invention can be dispersed or admixed toprovide a homogeneous medium. In addition, selection of one or moreflavoring adjuvants, as well as the quantities thereof will depend uponthe precise organoleptic character desired in the finished product.Thus, in the case of flavoring compositions, ingredient selection willvary in accordance with the foodstuff, chewing gum, medicinal product ortoothpaste to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount of thetrans, trans-Δ-damascone or composition containing a high proportion oftrans, trans-Δ-damascone and less than 50% of cis, trans-Δ-damasconeemployed in a particular instance can vary over a relatively wide range,depending upon the desired organoleptic effects to be achieved. Thus,correspondingly, greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored is relatively blandto the taste, whereas relatively minor quantities may suffice forpurposes of enhancing the composition merely deficient in natural flavoror aroma. The primary requirement is that the amount selected to beeffective, i.e., sufficient to alter, modify or enhance the organolepticcharacteristics of the parent composition, whether foodstuff per se,chewing gum per se, medicinal product per se, toothpaste per se, orflavoring composition.

The use of insufficient quantities of the compound trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of the compound trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone rangingfrom a small but effective amount, e.g., 0.5 parts per million up toabout 100 parts per million based on total composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended, since they fail to prove commensurate enhancement oforganoleptic properties. In those instances, wherein the compound trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone is addedto the foodstuff as an integral component of a flavoring composition, itis, of course, essential that the total quantity of flavoringcomposition employed be sufficient to yield an effective concentrationof the trans, trans-Δ-damascone or composition containing a highproportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the compound trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone in concentrations ranging fromabout 0.1% up to about 15% by weight based on the total weight of thesaid flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the compound trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone with, for example, gum arabic,gum tragacanth, carrageenan and the like, and thereafter spray-dryingthe resultant mixture whereby to obtain the particular solid product.Pre-prepared flavor mixes in powder form, e.g., a fruit-flavored powdermix are obtained by mixing the dried solid components, e.g., starch,sugar and the like and the compound trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone in a dry blender until therequisite degree of uniformity is achieved.

It is presently preferred to combine with the compound trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone of ourinvention, the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl Anthranilate;

5-Methyl furfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

β-Damascone (1-crotonyl-2,2,6-trimethylcyclohex-1-ene);

β-Damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,3-diene);

Beta-cyclohomocitral (2,2,6-trimethylcyclohex-1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene); and

2-(4-Hydroxy-4-methylpentyl) norbornadiene

The compound trans, trans-Δ-damascone or composition containing a highproportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone and one or more auxiliary perfume ingredients,including for example, alcohols, aldehydes, ketones, terpinichydrocarbons, nitriles, esters, lactones, natural essential oils andsynthetic essential oils, may be admixed so that the combined odors ofthe individual components produce a pleasant and desired fragrance,particularly and preferably in rose fragrances. Such perfumecompositions usually contain (a) the main note or the "bouquet" orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low boiling fresh smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the compoundtrans, trans-Δ-damascone or composition containing a high proportion oftrans, trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone canbe used to alter, modify or enhance the aroma characteristics of aperfume composition, for example, by utilizing or moderating theolfactory reaction contributed by another ingredient in the composition.

The amount of the trans, trans-Δ-damascone or composition containing ahigh proportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone of our invention which will be effective in perfumecompositions as well as in perfumed articles and colognes depends onmany factors, including the other ingredients, their amounts and theeffects which are desired. It has been found that perfume compositionscontaining as little as 0.01% of the trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone or even less (e.g., 0.005%) canbe used to impart a rose, berry, apple, green and sweet floral note tosoaps, cosmetics or other products. The amount employed can range up to70% of the fragrance components and will depend on considerations ofcost, nature of the end product, the effect desired on the finishedproduct and the particular fragrance sought.

The compound trans, trans-Δ-damascone or composition containing a highproportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone of our invention is useful [taken alone or togetherwith other ingredients in perfume compositions] as (an) olfactorycomponent(s) in detergents and soaps, space odorants and deodorants,perfumes, colognes, toilet water, bath preparations, such as creams,deodorants, hand lotions and sun screens; powders such as talcs, dustingpowders, face powders and the like. When used as (an) olfactorycomponent(s) as little as 1% of the trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone will suffice to impart anintense floral note to rose formulations. Generally, no more than 3% ofthe trans, trans-Δ-damascone or composition containing a high proportionof trans, trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone,base on the ultimate end product, is required in the perfumecomposition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the compound trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone. Thevehicle can be a liquid such as an alcohol, a non-toxic alcohol, anon-toxic glycol, or the like. The carrier can also be an absorbentsolid, such as a gum (e.g., gum arabic) or components for encapsulatingthe composition (such as gelatin).

It will thus be apparent that the compound trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone of our invention can be utilizedto alter, modify or enhance sensory properties, particularlyorganoleptic properties, such as flavor(s) and/or fragrance(s) of a widevariety of consumable materials.

Furthermore, the trans, trans-Δ-damascone or composition containing ahigh proportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone of our invention are capable of supplying and/orpotentiating certain flavor and aroma notes usually lacking in manytobacco flavors heretofore provided.

As used herein in regard to tobacco flavors, the terms "alter" and"modify" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland tobacco, tobacco substitutes, ortobacco flavor formulations or augmenting the existing flavorcharacteristic where a natural flavor is deficient in some regard orsupplementing the existing flavor impression to modify its quality,character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without change in kind of quality of aroma or taste) ofone or more taste and/or aroma nuances present in the organolepticimpression of tobacco or a tobacco substitute or a tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobaccoproduct and additives therefor, as well as methods of making the samewhich overcome specific problems heretofore encountered in whichspecific desired floral, musty, hay-tea-like, sweet and fruity aroma andtaste nuances thereof, are created or enhanced and may be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various floral, musty, hay-tea-like, sweet and fruity notes maybe imparted to smoking tobacco products and may be readily varied andcontrolled to produce the desired uniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient thetrans, trans-Δ-damascone or composition containing a high proportion oftrans, trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone ofour invention.

In addition to the trans, trans-Δ-damascone or composition containing ahigh proportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone of our invention, other flavoring and aroma additivesmay be added to the smoking tobacco materials or substitute thereforeither separately or in mixture with the trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone as follows:

(i) Synthetic Materials:

Beta-ethyl-cinnamaldehyde;

Beta-cyclohomocitral;

Eugenol;

Dipentene;

Damascenone;

Damascone;

Maltol;

Ethyl Maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1,b]-furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in

Example V of U.S. Pat. No. 3,589,372 issued on June 29, 1971.

(ii) Natural Oils:

Celery seed Oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg Oil;

Origanum Oil.

An aroma and flavoring concentrate containing the trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone and, ifdesired, one or more of the above-indicated additional flavoringadditives may be added to the smoking tobacco material, to the filter orto the leaf or paper wrapper. The smoking tobacco material may beshredded, cured, cased and blended tobacco material or reconstitutedtobacco material or tobacco substitutes (e.g., lettuce leaves) ormixtures thereof. The proportions of flavoring additives may be variedin accordance with taste but insofar as enhancement or the imparting ofnatural and/or sweet notes, we have found that satisfactory results areobtained if the proportion by weight of the sum total of the trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone to smokingtobacco material is between 250 ppm and 1,500 ppm (0.025%-0.15%) of theactive ingredients to the smoking tobacco material. We have furtherfound that satisfactory results are obtained if the proportion by weightof the sum total of the trans, trans-Δ-damascone or compositioncontaining a high proportion of trans, trans-Δ-damascone and less than50% of cis, trans-Δ-damascone used to flavoring material is between2,500 and 15,000 ppm (0.25%-1.5%).

Any convenient method for incorporating the trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone in the tobacco product may beemployed. Thus, the trans, trans-Δ-damascone or composition containing ahigh proportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone taken alone or along with other flavoring additivesmay be dissolved in a suitable solvent such as ethanol, pentane, diethylether and/or other volatile organic solvents and the resulting solutionmay either be sprayed on the cured, cased and blended tobacco materialor the tobacco material may be dipped into such solution. Under certaincircumstances, a solution of the trans, trans-Δ-damascone or compositioncontaining a high proportion of trans, trans-Δ-damascone and less than50% of cis, trans-Δ-damascone taken alone or taken further together withother flavoring additives as set forth above, may be applied by means ofa suitable applicator such as a brush or roller on the paper or leafwrapper for the smoking product, or it may be applied to the filter byeither spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the trans,trans-Δ-damascone or composition containing a high proportion of trans,trans-Δ-damascone and less than 50% of cis, trans-Δ-damascone in excessof the amounts or concentrations above-indicated so that when blendedwith other tobaccos, the final product will have the percentage withinthe indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of the trans, trans-Δ-damascone or composition containing ahigh proportion of trans, trans-Δ-damascone and less than 50% of cis,trans-Δ-damascone in an amount to provide a tobacco compositioncontaining 800 ppm by weight of the trans, trans-Δ-damascone orcomposition containing a high proportion of trans, trans-Δ-damascone andless than 50% of cis, trans-Δ-damascone on a dry basis. Thereafter, thealcohol is removed by evaporation and the tobacco is manufactured intocigarettes by the usual techniques. The cigarette when treated asindicated has a desired and pleasing aroma (increased smoke bodysensation in the mouth with enhanced tobacco-like notes and pleasantaromatic nuances) which is detectable in the main and side streams whenthe cigarette is smoked. This aroma is described as having floral,musty, hay-tea-like, sweet and fruity notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, the trans, trans-Δ-damascone or compositioncontaining a high proportion of trans, trans-Δ-damascone and less than50% of cis, trans-Δ-damascone of our invention can be incorporated withmaterials such as filter tip materials, seam paste, packaging materialsand the like which are used along with tobacco to form a product adaptedfor smoking. Furthermore, the trans, trans-Δ-damascone or compositioncontaining a high proportion of trans, trans-Δ-damascone and less than50% of cis, trans-Δ-damascone can be added to certain tobaccosubstitutes of natural or synthetic origin (e.g., dried lettuce leaves)and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

The following Example I serves to illustrate the prior art. Thefollowing Examples II-IX serve to illustrate our invention.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Preparation of Composition Containing High Proportion of Cis,Trans-Δ-Damascone (According to Ayyar, et al)

Reaction Sequence: ##STR15##

Procedure:

Part A: Preparation of Mixture of Major Proportion ofTrans-4-Acetyl-3,5,5-Trimethylcyclohexene and Low Proportion of CisIsomer

To powdered anhydrous aluminum chloride (13.7 g, 0.10 mol) undernitrogen is added dry dichloromethane (30 ml). Mesityl oxide (20.0 g,0.20 mol) in dichloromethane (75 ml) is then added with stirring over 30minutes and the mixture is heated under reflux for 1 hour.Penta-1,3-diene (mixture of isomers) (70.0 g, 1.03 mol) indichloromethane (300 ml) is added dropwise over 6 hours. The mixture isthen stirred overnight at room temperature. Liquid paraffin (100 ml) and10% hydrochloric acid (200 ml) is added and the mixture is steamdistilled for 3 hours. The steam distillate is extracted with ether(5×75 ml) and the product worked up as usual. The residue is distilledto give a liquid, b.p. 52°-54° at 1 mm Hg (15.0 g, 0.09 mol, 45%), shownby GLC [column (A), 120° C.] to consist of two components in theporportions ca. 13:87 in order of increasing retention time. These wereseparated by preparative GLC [column (B), 130° C.]:trans-4-acetyl-3,5,5-trimethylcyclohexene (6) (Found: C, 79.6; H, 10.75.C₁₁ H₁₈ O requires C, 79.5; H, 10.85%); m/e 166 (M⁺, 33%), 123 (100),109 (39), 107 (33), 81 (39), 69 (33), 67 (27), 55 (27), 43 (82) and 41(50); τ9.17-8.86 (9H, 4 overlapping lines, 3- and 5-Me), 8.60-8.04 (2H,m, 6-H₂), 7.87 (3H, s, Ac), 7.90-7.30 (2H, m with br s overlapping, 3-and 4-H), and 4.54 br (2H, s, 1- and 2-H); ν_(max). (film) 1 710 (Ac)and 695 cm⁻¹ (cis--CH═CH); cis-4-acetyl-3,5,5-trimethylcyclohexene (5)(Found: C, 79.55; H, 10.8%); m/e 166 (M⁺, 4%), 138 (39), 123 (95), 109(11), 107 (23), 81 (12), 69 (8), 67 (9), 55 (12), 53 (11), 43 (100) and41 (23); τ9.18-8.89 (9H, 3 overlapping lines, 3- and 5-Me), 8.68-8.18(2H, m, 6-H₂), 7.97 (3H, s, Ac), 7.70-7.30 (2H, m, 4- and 3-H), and4.86-4.16 (2H, m, 1- and 2-H); ν_(max). (film) 1 710 (Ac), 1 692 and 710cm⁻¹ (cis--CH═CH).

Part B: Preparation of Cis, Trans-Δ-Damascone

The resulting mixture of 4-acetyl-3,5,5-trimethylcyclohexenes (mixtureof trans and cis stereoisomers with the trans isomer predominating) aretreated with acetaldehyde and the resultant mixture is dehydratedaccording to the following procedure:

To a solution of ethyl magnesium bromide [from magnesium turnings, 0.92grams, and ethyl bromide, 4.20 grams, in dry ether, 10 ml] N-methylaniline, 4.1 grams, in dry benzene, 5 ml, is added with stirring andcooling. The 4-acetyl-3,5,5-trimethylcyclohexene isomer mixture producedin Part A, 5.00 grams, in benzene, 5 ml, is added to the cooled mixturewhich is stirred at room temperature for 30 minutes and then cooledwhile acetaldehyde, 1.90 grams in benzene, 10 ml, is added during the 20minute period. The mixture is stirred for a further 30 minutes at 0° C.and then poured into ice (20 grams) and 10% hydrochloric acid (50 ml).The mixture is extracted with petroleum (5×50 ml) and the combinedextracts are washed with 10% hydrochloric acid (5×50 ml) and worked up.The residue (6.00 g) is diluted with dry benzene (100 ml) andparatoluenesulfonic acid (0.20 grams) is added. The mixture is heatedunder reflux and the water formed is removed azeotropically in a DeanStark apparatus. Distillation of the dehydrated product under reducedpressure yields a mixture of the isomers of Δ-damascone, a highproportion of cis, trans-Δ-damascone and a low proportion of trans,trans-Δ-damascone. B.p. 65°-67° at 0.6 mm Hg (2.8 g, 15 mmol, 50%)(Found: C, 81.2; H, 10.3. C₁₃ H₂₀ O requires C, 81.25; H, 10.4%); m/e192 (M⁺, 48%), 177 (17), 137 (13), 123 (56), 109 (21), 107 (19), 91(15), 93 (15), 81 (36), 69 (100), 55 (17) and 41 (52); τ9.12 and 9.03(9H, 2s, 6-Me₂ overlapping the d due to 2-Me), 8.16 (3H, dd, J 6.5 and 1Hz, --C═C--CH₃), 8.40-7.22 (4H, m, ring 5-H₂, 1-H, and 2-H), 4.72-4.22(2H, m, ring 3- and 4-H), 3.93 (1H, dq, J 16 and 1 Hz, --CO--CH═C), and3.29 (1H, dq, J 6.5 and 16 Hz, --C═CH--CH₃); ν_(max). (film) 1 695, 1665, 1 630 (--CH═C--CO--), and 970 cm⁻¹ (trans--CH═CH); λ_(max).(cyclohexane) 223 nm (ε10 100).

The Mass Spectral analysis is as follows:

    ______________________________________                                        m/e         Relative Intensity                                                ______________________________________                                        41          10.sup.6                                                          69          100.sup.0                                                         81          20.sup.4                                                          83          7                                                                 107         8                                                                 108         7                                                                 109         13.sup.5                                                          123         34.sup.2                                                          177         7                                                                 M192        20.sup.3                                                          ______________________________________                                    

FIG. 1 sets forth the NMR spectrum of cis, trans-Δ-damascone. FIG. 2sets forth the Infrared spectrum of cis, trans-Δ-damascone.

EXAMPLE II Preparation of Trans, Trans-Δ-Damascone

Reaction Sequence: ##STR16##

Procedure:

Part A: Preparation of 1-α-Acetyl-2-β, 6,6-Trimethyl-3-Cyclohexene

To a 1 liter receiver equipped with magnetic stirrer, reflux condenser,heating mantle and thermometer, is added 34.6 g 1-α-acetyl-2-β,6,6-trimethyl-cis-3-cyclohexene, 500 ml ethanol (food grade) and 10 gpotassium hydroxide. This mixture is then refluxed with stirring for 25hours. The alcohol is then removed by rotary evaporator and the residuedissolved in ether (150 ml) and washed five times with saturated sodiumchloride solution (25 ml portion) and is then dried over magnesiumsulfate. 33.7 g of the resulting crude product is distilled to give 11fractions, all of which contained ˜80% of product, 1-α-acetyl-2-β,6,6,-trimethyl-3-cyclohexene having the structure: ##STR17##

Yield of conversion: 74%.

Part B: Preparation of Trans, Trans-Δ-Damascone

To a 500 ml three necked reaction flask equipped with magnetic stirrer,addition funnel, thermometer, reflux condenser, nitrogen purge, heatingmantle and isopropanol cooling bath, is added:

    ______________________________________                                        6        g           magnesium turnings                                       50       ml          anhydrous ether                                          ______________________________________                                    

To the magnesium turnings, via addition funnel, is added 26 g of ethylbromide in 50 ml of dry ether. After addition the mixture is refluxedfor 1/2 hour. The mixture is then cooled to 0° C. and 25 g ofN-methylaniline in 30 ml of dry benzene is added over a 1/2 hour period.1-α-Acetyl-2-β, 6,6-trimethyl-3-cyclohexane (30 g) in 30 ml of benzeneis added dropwise over a 45 minute period at 0°-5° C. and is then warmedup to room temperature (24° C.) and stirred for 1/2 hour. The mixture isthen cooled again to 0° C. while redistilled acetaldehyde (12 g) in 50ml of benzene is added over a 30 minute period. The mixture is thenstirred for 1 hour at 0° C. and then poured into 200 g of ice containing100 ml 10% hydrochloric acid. The mixture is then extracted five timeswith petroleum ether (50 ml portion) and the extracts are combined andwashed two times with 10% hydrochloric acid (50 ml) and five times withsaturated sodium chloride (50 ml) and dried over MgSO₄. After thesolvent is evaporated, 37.1 g of crude material resulted.

The crude keto alcohol (37.1 g) in 500 ml of anhydrous benzene is addedto a 1 liter flask containing 1 gram of paratoluenesulfonic acid. Thismixture is refluxed for 8 hours while 3 mls of water is removed via aBidwell trap. The crude material in benzene solution is then washedthree times with 10% Na₂ CO₃ (100 ml portions) and four times withsaturated NaCl solution (100 ml portions), dried and the solventremoved. This material is then distilled on a micro-Vigreux column toyield 13 fractions. Fractions 4-13 (20.1 g) are combined for columnchromatography to remove the starting material, α-acetyl-2-β,6,6-trimethyl-3-cyclohexene.

The material is purified by column chromatography over silica gel(deactivated by 5% water) then redistilled to yield product having thestructure: ##STR18## having a purity of 93% (the other 7% consists of 5%cis, trans isomer and 2% unidentified product).

The Mass Spectral analysis for trans, trans-Δ-damascone is as follows:

    ______________________________________                                        m/e         Relative Intensity                                                ______________________________________                                        41          14.sup.5                                                          69          100.sup.1                                                         70          9                                                                 81          22.sup.4                                                          107         11.sup.6                                                          109         9                                                                 121         8                                                                 122         8                                                                 123         38.sup.2                                                          M192        31.sup.3                                                          ______________________________________                                    

FIG. 3 represents the NMR spectrum for trans, trans-Δ-damascone,Fraction 6. FIG. 4 represents the Infrared spectrum for trans,trans-Δ-damascone, Fraction 6.

EXAMPLE III Comparison of Perfume Compositions Containing Product ofExample I Containing a High Proportion of Cis, Trans-Δ-Damascone andComposition of Example II Containing a High Proportion of Trans,Trans-Δ-Damascone

The trans, trans-Δ-damascone has a fine tobacco-rose, appley, berrynote. The cis, trans-Δ-damascone isomer, on the other hand, is floralbut with a camphoraceous, mintyness which renders it less desirable as aperfumery material. This difference is seen quite readily when theabove-mentioned Δ-damascones are compared in an actual fragrancecomposition, wherein 3% of a 10% solution in diethyl phthalate is used.The following rose perfume demonstrates the effect:

    ______________________________________                                        Ingredient         I      II     III                                          ______________________________________                                        Rhodinol           250    250    250                                          Phenylethyl alcohol                                                                              195    195    195                                          Alpha methyl ionone                                                                              80     80     80                                           Linalyl acetate    60     60     60                                           Cis-3-hexenyl acetate                                                                            5      5      5                                            Jasmine absolute   10     10     10                                           Cinnamic alcohol   20     20     20                                           Rhodinyl acetate   60     60     60                                           Cyclohexyl ethyl alcohol                                                                         20     20     20                                           Geraniol           130    130    130                                          Geranyl acetate    80     80     80                                           Paraisopropyl cyclohexanol                                                                       60     60     60                                           Diethyl phthalate  30     --     --                                           Cis, trans-Δ-damascone (10% in                                          diethyl phthalate) --     30     --                                           Trans, trans-Δ-damascone (10%                                           in diethyl phthalate)                                                                            --     --     30                                                              1000   1000   1000 Total                                   ______________________________________                                    

The trans, trans-Δ-damascone lends a sweet floral rose note to thefragrance composition. On the other hand, the cis, trans isomer could besaid to have ruined the perfume, giving it a very rough musty topnotewhich is not desirable in perfume compositions. The undesirablecharacter of the cis, trans isomer is enhanced by its use in thefragrance. This effect is not expected.

The desirable trans, trans-Δ-damascone may be used in perfumecompositions at from 0.05 up to 25%. Larger amounts may be used forspecial effects.

EXAMPLE IV Comparison of Soaps Containing Product of Example I,Containing a High Proportion of Cis, Trans-Δ-Damascone Versus Product ofExample II Containing a High Proportion of Trans, Trans-Δ-Damascone

Both the trans, trans and the cis, trans were incorporated into soap(LVU-1) at 0.1% by weight. After two weeks in the oven at 90° F., bothisomers showed no visual effect from the heat. On the other hand, theodor of the trans, trans was far superior to the cis, trans which had aharsh camphoraceous topnote and may be considered unsuitable for soapperfumery.

EXAMPLE V Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the trans, trans-Δ-damascone produced according toExample II. It has an excellent rose, berry, apple, green and sweetfloral note.

EXAMPLE VI Perfumed Liquid Detergent

Concentrated liquid detergents with rose, berry, apple, green and sweetfloral notes (which detergents are produced from Lysine salt ofn-dodecyl benzene sulfonic acid as more specifically described in U.S.Pat. No. 3,948,818, issued on Apr. 6, 1976) are prepared containing thetrans, trans-Δ-damascone prepared according to Example II. They areprepared by adding and homogeneously mixing the appropriate quantity ofthe trans, trans-Δ-damascone in the liquid detergent. The detergents allpossess a rose, berry, apple, green and sweet floral note, the intensityincreasing with greater concentrations of the trans, trans-Δ-damascone.

EXAMPLE VII Preparation of a Cologne and Handkerchief Perfume

The trans, trans-Δ-damascone prepared according to Example II isincorporated in a cologne at a concentration of 2.5% in 85% aqueousethanol; and into a handkerchief perfume at a concentration of 20% (in95% aqueous ethanol). A distinct and definite rose, berry, apple, greenand sweet floral note is imparted to the cologne and to the handkerchiefperfume.

EXAMPLE VIII Raspberry Flavor Formulation

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Vanillin             2.0                                                      Maltol               5.0                                                      Parahydroxybenzylacetone                                                                           5.0                                                      Alpha-ionone (10% in propylene                                                glycol)              2.0                                                      Ethyl butyrate       6.0                                                      Ethyl acetate        16.0                                                     Dimethyl sulfide     1.0                                                      Isobutyl acetate     13.0                                                     Acetic acid          10.0                                                     Acetaldehyde         10.0                                                     Propylene glycol     930.0                                                                         1000.0                                                   ______________________________________                                    

Trans, trans-Δ-damascone is added to half of the above formulation atthe rate of 0.2%. The formulation with the trans, trans-Δ-damascone iscompared with the formulation without the trans, trans-Δ-damascone atthe rate of 0.01% (100 ppm) in water and evaluated by a bench panel.

The flavor containing the trans, trans-Δ-damascone is found to have asubstantially more pleasant and better raspberry aroma. It is theunanimous opinion of the bench panel that the chemical, trans,trans-Δ-damascone rounds the flavor out and contributes to a verynatural fresh aroma and taste as found in full ripe raspberries.Accordingly, the flavor with the addition of the trans,trans-Δ-damascone is considered as substantially better than the flavorwithout trans, trans-Δ-damascone.

EXAMPLE IX Tobacco Formulation

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Bright         40.1                                                           Burley         24.9                                                           Maryland       1.1                                                            Turkish        11.6                                                           Stem (flue-cured)                                                                            14.2                                                           Glycerine      2.8                                                            Water          5.3                                                            ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above-stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 or 1,000ppm of the mixture produced according to Example II of trans,trans-Δ-damascone. The control cigarettes not containing the mixture oftrans, trans-Δ-damascone produced according to the process of Example IIand the experimental cigarettes which contain the mixture of trans,trans-Δ-damascone produced according to Example II are evaluated bypaired comparison and the results are as follows:

The experimental cigarettes are found to have more body in tobacco smokeflavor and a fuller body sensation. The tobacco-like notes are enhancedand the flavor of the tobacco on smoking is more aromatic with floral,musty, hay-tea-like, sweet and fruity aroma and taste nuances.

The tobacco smoke flavor of the experimental cigarettes, prior tosmoking, has floral, musty, hay-tea-like, sweet and fruity notes. Allcigarettes are evaluated for smoke flavor with a 20 mm cellulose acetatefilter.

EXAMPLE X Large Scale Preparation of Trans, Trans-Δ-Damascone

Reaction Sequence: ##STR19##

Procedure:

Part A: Preparation of 1-α-Acetyl-2-β, 6,6-Trimethyl-3-Cyclohexene

To a 3 liter glass reactor equipped with magnetic stirrer, refluxcondenser, heating mantle and thermometer, is added 1056 g anhydrous CH₃OH. 44 Grams of sodium metal is then added slowly to the methanol whilemaintaining the temperature at 25° C. 1085 Grams of 1-α-acetyl-2-β,6,6-trimethyl-cis-3-cyclohexene is then added to the reaction mixture.This mixture is then refluxed with stirring for 24 hours. 120 Grams ofacetic acid is then added to the reaction mass. The reaction mass isthen washed with one equal volume of water and one liter of saturatedsodium chloride solution. Crude weight is 1040 grams. The resultingproduct is distilled in a 1 foot porcelain saddle packed column yieldingthe following fractions:

    ______________________________________                                        Fraction                                                                             Vapor Temp-                                                                              Liquid Temp-                                                                             Vacuum Weight of                                 No.    erature    erature    mm Hg  Fraction                                  ______________________________________                                        1      38-81      88-94      9.0    42.0                                      2      85         100        9.0    244.0                                     3      86         100        9.0    99.0                                      4      86         102        9.0    114.0                                     5      87         102        9.0    107.0                                     6      90         110        11.0   96.0                                      7      90         110        11.0   99.0                                      8      97         120        11.0   88.0                                      9      120        135        11.0   --                                        ______________________________________                                    

Fractions 2-7 are combined and used as product (847 grams b.p. 85°-90°C. at 9-11 mm pressure).

The product is substantially 1-α-acetyl-2-β, 6,6-trimethyl-3-cyclohexenehaving the structure: ##STR20##

Part B: Preparation of Trans, Trans-Δ-Damascone

To a 1 liter three necked reaction flask equipped with magnetic stirrer,addition funnel, thermometer, reflux condenser, nitrogen purge, heatingmantle and isopropanol cooling bath, is added 365 ml (1.1 moles) ofmethyl magnesium chloride. 168 Grams (1.1 moles) of N-methyl aniline isthen slowly added to the methyl magnesium chloride while maintaining thetemperature at 30° C. Following the addition of the N-methyl aniline, 75ml additional CH₃ MgCl (methyl magnesium chloride) is added. Over aperiod of 15 minutes, 1-α-acetyl-2-β, 6,6-trimethyl-3-cyclohexene (200grams/1.0 moles) is added to the reaction mass while maintaining thetemperature at 30°-34° C. with cooling. Following the addition of1-α-acetyl-2-β, 6,6-trimethyl-3-cyclohexene, the reaction mass is cooledto 0° to -5° C. and while maintaining the reaction mass temperature at0° to -5° C., 49 grams (1.1 moles) of acetaldehyde dissolved in 120 mlof toluene is added to the reaction mass. Following the acetaldehydeaddition, 10% aqueous hydrochloric acid is added and the aqueous layeris separated from the organic layer. The organic layer is stripped ofsolvent at 35° C. under vacuum yielding a crude material weighing 240grams.

To the 240 grams of the resulting intermediate, is added 150 ml aceticanhydride and 25 grams of sodium acetate in a 500 ml reaction flask. Theresulting reaction mixture is heated to 100°-115° C. over a period of 3hours. At the end of the 3 hour heating period the reaction mass iscooled to 80° C. and an equal volume of water is added to destroy theexcess acetic anhydride. The organic layer is separated from the aqueouslayer and the organic layer is washed with an equal volume of water andan equal volume of saturated sodium bicarbonate. The organic layer isthen stripped of solvent and distilled to yield the following fractions:

    ______________________________________                                               Vapor   Liquid                                                         Fraction                                                                             Temp-   Temp-    Vacuum Reflux                                                                              Weight of                                No.    erature erature  mm Hg  Ratio Fraction                                 ______________________________________                                        1      51-53   83-99    2.2-   4:1   15.2                                                             2.7                                                   2      53      100      1.8    4:1   12.5                                     3      72      102      1.7    4:1   11.3                                     4      77-85   101-104  2.5-   4:1   7.4                                                              2.6                                                   5      87      105      2.5    4:1   21.3                                     6      91      108      3.9    1:1   27.3                                     7      87      110      3.1    1:1   26.5                                     8      87      119      3.1    1:1   24.7                                     9      87      125      3      1:1   11.02                                    10     88      135      3      1:1   4.3                                      11     81      250      3      1:1   8.2                                      ______________________________________                                    

after adding to the mixture to be distilled 44.7 grams of Primol® and0.4 grams of Ionox®. Fractions 5-10 are combined and used as product(123 grams b.p. 87°-88° C. at 3.0 mm pressure). Spectral tests confirmthat the resulting product has the structure: ##STR21##

The Mass Spectral analysis for trans, trans-Δ-damascone is as follows:

    ______________________________________                                        m/e         Relative Intensity                                                ______________________________________                                        41          14.sup.5                                                          69          100.sup.1                                                         70          9                                                                 81          22.sup.4                                                          107         11.sup.6                                                          109         9                                                                 121         8                                                                 122         8                                                                 123         38.sup.2                                                          M192        31.sup.3                                                          ______________________________________                                    

FIG. 3 represents the NMR spectrum for trans, trans-Δ-damascone,Fraction 6. FIG. 4 represents the Infrared spectrum for trans,trans-Δ-damascone, Fraction 6.

EXAMPLE XI Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the trans, trans-Δ-damascone produced according toExample X. It has an excellent rose, berry, apple, green and sweetfloral note.

EXAMPLE XII Perfumed Liquid Detergent

Concentrated liquid detergents with rose, berry, apple, green and sweetfloral notes (which detergents are produced from Lysine salt ofn-dodecyl benzene sulfonic acid as more specifically described in U.S.Pat. No. 3,948,818, issued on Apr. 6, 1976) are prepared containing thetrans, trans-Δ-damascone prepared according to Example X. They areprepared by adding and homogeneously mixing the appropriate quantity ofthe trans, trans-Δ-damascone in the liquid detergent. The detergents allpossess a rose, berry, apple, green and sweet floral note, the intensityincreasing with greater concentrations of the trans, trans-Δ-damascone.

EXAMPLE XIII Preparation of a Cologne and Handkerchief Perfume

The trans, trans-Δ-damascone prepared according to Example X isincorporated in a cologne at a concentration of 2.5% in 85% aqueousethanol; and into a handkerchief perfume at a concentration of 20% (in95% aqueous ethanol). A distinct and definite rose, berry, apple, greenand sweet floral note is imparted to the cologne and to the handkerchiefperfume.

EXAMPLE XIV Raspberry Flavor Formulation

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Vanillin             2.0                                                      Maltol               5.0                                                      Parahydroxybenzylacetone                                                                           5.0                                                      Alpha-ionone (10% in propylene                                                glycol)              2.0                                                      Ethyl butyrate       6.0                                                      Ethyl acetate        16.0                                                     Dimethyl sulfide     1.0                                                      Isobutyl acetate     13.0                                                     Acetic acid          10.0                                                     Acetaldehyde         10.0                                                     Propylene glycol     930.0                                                                         1000.0                                                   ______________________________________                                    

Trans, trans-Δ-damascone produced according to Example X is added tohalf of the above formulation at the rate of 0.2%. The formulation withthe trans, trans-Δ-damascone is compared with the formulation withoutthe trans, trans-Δ-damascone at the rate of 0.01% (100 ppm) in water andevaluated by a bench panel.

The flavor containing the trans, trans-Δ-damascone is found to have asubstantially more pleasant and better raspberry aroma. It is theunanimous opinion of the bench panel that the chemical, trans,trans-Δ-damascone rounds the flavor out and contributes to a verynatural fresh aroma and taste as found in full ripe raspberries.Accordingly, the flavor with the addition of the trans,trans-Δ-damascone is considered as substantially better than the flavorwithout trans, trans-Δ-damascone.

EXAMPLE XV Tobacco Formulation

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Bright         40.1                                                           Burley         24.9                                                           Maryland       1.1                                                            Turkish        11.6                                                           Stem (flue-cured)                                                                            14.2                                                           Glycerine      2.8                                                            Water          5.3                                                            ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate .05                                                            Ethyl valerate .05                                                            Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above-stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 or 1,000ppm of the mixture produced according to Example X of trans,trans-Δ-damascone. The control cigarettes not containing the mixture oftrans, trans-Δ-damascone produced according to the process of Example Xand the experimental cigarettes which contain the mixture of trans,trans-Δ-damascone produced according to Example II are evaluated bypaired comparison and the results are as follows:

The experimental cigarettes are found to have more body in tobacco smokeflavor and a fuller body sensation. The tobacco-like notes are enhancedand the flavor of the tobacco in smoking is more aromatic with floral,musty, hay-tea-like, sweet and fruity aroma and taste nuances.

The tobacco smoke flavor of the experimental cigarettes, prior tosmoking, has floral, musty, hay-tea-like, sweet and fruity notes. Allcigarettes are evaluated for smoke flavor with a 20 mm cellulose acetatefilter.

EXAMPLE XVI Preparation of a Detergent Composition

A total of 100 grams of a detergent powder (a non-ionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.15grams of trans, trans-Δ-damascone prepared according to Example X untila substantially homogeneous composition is obtained. This compositionhas an excellent rose, berry, apple, green and sweet floral aroma.

EXAMPLE XVII Perfumed Liquid Detergents

Concentrated liquid detergents with rich, pleasant rose, berry, apple,green and sweet floral aromas are prepared containing 0.10%, 0.15% and0.20% of trans, trans-Δ-damascone prepared according to Example X. Theyare prepared by adding and homogeneously admixing the appropriatequantity of trans, trans-Δ-damascone prepared according to Example X inthe liquid detergent. The liquid detergents are all produced usinganionic detergents containing a 50:50 mixture of sodium lauroylsarcosinate and potassium N-methyl lauroyl taruide. The detergents allpossess a pleasant rose, berry, apple, green and sweet floral fragrance,the intensity increasing with greater concentration of trans,trans-Δ-damascone prepared according to Example X of this invention.

What is claimed is:
 1. A process for producing a composition of matter comprising more than 80% trans, trans-delta-damascone comprising the steps of (i) intimately admixing 1-alpha-acetyl-2-alpha-6,6-trimethyl-3-cyclohexene with refluxing alcoholic base or alkali metal alcoholate according to the reaction: ##STR22## wherein R is lower alkyl, selected from the group consisting of methyl and ethyl and M is alkali metal selected from the group consisting of sodium and potassium; (ii) fractionally distilling the resulting reaction mass whereby a composition of matter containing more than 80% by weight of the trans isomer of 1-acetyl-2,6,6-trimethyl-3-cyclohexane is isolated; (iii) intimately admixing the resulting distillate containing more than 80% of the trans isomer of 1-acetyl-2,6,6-trimethyl-3-cyclohexane and less than 20% of the cis isomer of 1-acetyl-2,6,6-trimethyl-3-cyclohexane with acetaldehyde yielding a composition of matter containing more than 80% of the trans isomer of the hydroxy ketone having the structure: ##STR23## (iv) dehydrating the resulting product with a dehydrating agent selected from the group consisting of paratoluene sulphonic acid and acetic anhydride whereby trans,trans-delta-damascone is produced according to the reaction: ##STR24## (v) distilling from the reaction mass a material containing 80-98% trans,trans-delta-damascone and 2-20% cis,trans-delta-damascone.
 2. The process of claim 1 comprising the additional step of physically separating 100% trans,trans-delta-damascone from the resulting mixture. 